Process for breaking petroleum emulsions



Patented May 25, 1954 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City,

to Petrolite Mo., assignor Corporation, Wilmington, Del.,.a

corporation of Delaware N Drawing. Application June 27, 1952,

Serial No. 296,087

14 Claims. 1

This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the Water-inoil'type, and particularly petroleum emulsions.

The present invention is a continuation-inpart of my copending application, Serial No. 288,746, filed May 19, 1952.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as roily oil, cut oil, emulsified oil, etc., and which comprise fine droplets of naturallyoccurring Waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or Weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

The demulsifying agents employed in the present demulsifying process are the products obtained by the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, lowstage phenol-aldehyde resin of the type described hereinafter as component (a) in Part 1; (b) cyclic amidines of the type described hereinafter as component (b) in Part 1, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to with the equal weight there will be two phases on vigorous shaking eliminate Water and below the pyrolytic point 7 of the reactants and resultants 0f reaction; and with the proviso thatthe resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., in combination with water or particularly in the form of a salt of a low molal organic acid such as the acetate or hydroxy acetate, have sufiiciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et a1. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensaand surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Reference is again made to U. S. Patent 2,499,368, dated March Keiser. patent the following test appears:

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called subsurface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. lSuch 5050 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient'to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-in- Water type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking.

and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

appropriate product being Such test is obviously the same for the reason that- '7, 1950, to De Groote and In said immediately aforementioned In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethyl ether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surfaceactive characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an eq 'valent water-insoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction miX- ture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

For convenience, what is said hereinafter will be divided into five parts:

Part 1 is the introductory part as far as the demulsifying agents themselves are concerned, 1. e., the amine-modified resins;

Part 2 is concerned with the general structure of the amine-modified resin and also the resin itself, which is used as a raw material;

Part 3 is concerned with appropriate basic substituted irnidazolines and substituted tetrahydropyrimidines which conform to the previously noted requirements, 1. e., the presence of at least one basic secondary amino radical and freedom from any primary amino radical, and which are suitable in the preparation of the herein described amine modified resins;

Part 4 is concerned with the reactions involving the resin, the basic rin compound, and formaldehyde to produce the specific products or compounds; and

Part 5 is concerned with the use of the oilmodified resins obtained as described in Part 4 4 for the resolution of emulsions of the water-inoil type.

PART 1 As previously stated, this invention is concerned with the use as demulsifiers for resolution or breaking of petroleum emulsions of the waterin-oil type of certain amine-modified resins. Such amine-modified resins have been described in the aforementioned copending application, Serial No. 288,746, filed May 19, 1952.

The demulsifying agents are heat-stable oxyalkylation-susceptible resinous condensation products of (a) a defined phenol-aldehyde resin, (b) a defined cyclic amidine, and (c) formaldehyde. The condensation reaction is conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and the resultants of reaction. Another aspect of the invention, of course, is the procedure for making such condensation products.

The phenol-aldehyde resin designated as component (a) is an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. The phenol-aldehyde resin is difunctional only in regard to methylol-forming reactivity, and the resin is derived by reaction between a difunctional monohydric phenol and an aldehyde havin not over 8 carbon atoms and reactive toward the phenol. Also, the resin is formed in the substantial absence of trifunctional phenols. The phenol constituent of the resin is of the formula:

in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

The cyclic amidine designated as component (b) is selected from the class consisting of substituted unidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical. The amidine is also characterized by freedom from any primary amino radical.

This invention in a more limited aspect relates to the use as demulsifiers of certain aminemodified thermoplastic phenol-aldehyde resins. For purpose of simplicity the invention, as far as demulsification is concerned, may be typified by reference to the resinous materials themselves. These resins may be exemplified by an idealized formula which may, in part, be an over-simplification in an effort to present certain resin structure. Such formula would be the following:

in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from either a substituted imidazoline or a substituted tetrahydropyrimidine as previously specified and may be indicated thus:

in which HN represents amino group and two occurrences of R represent the remainder of the molecule. Stated another way, what has been depicted in the above formula is an oversimplifi'cation as far as the ring compound is concerned which is obvious by reference to a more elaborate formula depicting the actual structure of typical members of the group, such as:

2-heptadecyl,1-methylaminoethyl tetrahydropyrimidine The introduction of two such ring compound radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the product in a number of Ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe elTect or one in which the hydrophobe efiect more than counterbalances the hydrophile eifect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another effeet is introduced, particularly another hydrophile efiect. In such instances where there are hydroxyl groups present, needless to say there is a further hydrophile efiect introduced.

Combinations, resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines, particularly amines having secondary amino groups. Generally speaking, such materials have fallen into three classes; the first represents non-resinous combinations derived from phenols as such; the second class represents resins which are usually insoluble and used for the Purpose for which ordinary resins, particularly thermo-setting resins are adapted. The third class represents resins which are soluble as-initially prepared but are not heat-stable, i. e., they a reactive secondary terminal groups which are heat-convertible, which means they are not particularly suited as raw materials for subsequent chemical reaction which requires temperatures above the boiling point of water or thereabouts.

The third class of material which of the three classes mentioned approaches the closest to the herein-described derivatives or resinous amino derivatives is described in U. S. Patent No. 2,031,557, dated February 18, 1936, to Bruson. The procedure described in said Bruson patent apparently is concerned with the use of monoamines only.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols. This is a difierentiation from the resins described in the aforementioned Bruson patent, N 0. 2,031,557, insofar that said patent discloses suitable resins obtained from meta-substituted phenols, hydroxybenzene, resorcinol, p,p (dihydroxydiphenyl)dimethylmethane, and the like, all of which have at least three points of reaction per phenolic nuclei and as a result can yield resins which may be at least incipiently cross-linked even though they are apparently still soluble in oxygenated organic solvents or else are heat-reactive insofar that they may approach insolubility or become insoluble due to the elfect of heat, or added formaldehyde, or both.

The resins herein employed contain only two are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is Well known, although one may start with difunctional phenols, and depending on the procedure emobtain crosslinking which indicates that one or more of th phenolic nuclei have been converted from a, difunctional radical to a trifunctiona1 radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, .butyl, or the like, shifts from an ortho position to a meta position, or from a para, position to a meta position. For instance, in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

Apparently there is no similar limitation in regard to the resins employed in the aforementioned Bruson Patent 2,031,577, for the reason that one may prepare suitable resins from phenols of the kind already variably and inevitably would a functionality greater than resin molecule.

The resins herein employed are soluble in a non-oxygenated hydrocarbon solvent, such as benzene or xylene. As pointed out in the aforementioned Bruson Patent 2,031,557, one of the objectives is to convert the phenol-aldehyde resins employed as raw materials in such a way as to render them hydrocarbon soluble, i. e., soluble in benzene. The original resins of U. S. Patent 2,031,557 are selected on the basis of solubility in an oxygenated inert organic solvent, such as yield a resin having two in the ultimate specified which in alcohol or dioxane. It is immaterial whether the resins here employed are soluble in dioxane or alcohol, but they must be soluble in benzene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule. The resins employed in the aforementioned U. S. Patent No. 2,031,557, apparently need not meet any such limitations.

The condensation products here obtained, whetherin the form of the free base or the salt, do not go over to the insoluble stage on heating. This apparently is not true of the materials described in aforementioned Bruson Patent 2,031,577 and apparently one of the objectives with which the invention is concerned, is to obtain a heat-convertible condensation product. The condensation product obtained according to the present invention is heat stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass.

Although these condensation products have been prepared primarily with the thought in mind that they are percursors for subsequent reaction, yet as suchand without further reaction, they have definitely valuable properties and uses as hereinafter pointed out.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensationv products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to 140 to 150 C. If one were using resins of the kind described in U. S. Patent No. 2,031,557 it appears desirable and perhaps absolutely necessary that the temperature be kept relatively low, for instance, between C. and 100 C., and more'specifically at a temperature of 80 to 90 C. Therev is no such limitation in the condensation procedure herein described for reasons which are obvious in light of what has been said previously.

Whatis said abovedeserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. As pointed out in the instant invention the resin selected is Xylene or benzene soluble, which differentiates the resins from those employed in the aforementioned Bruson Patent No. 2,031,557. Since formaldehyde generally is employed economically in an aqueous phase to l0% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C. or 0., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of'glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, 1. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of 4 a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula R n R In the above formula 11. represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described inthe literature. A limited subgenus is in the instance of low molecular weight polymers wherethe total number of phenol nuclei varies from 3-to- 6;i. e., n varies from 1 to l; R represents'an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehydeit may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. .However, even when obtained froma .difunctional phenol, for instance para- No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized oversimplification previously referred to, the resultant product might be illustrated thus:

R! OH [OH I OH R! H H H H o- C-N R!/ H H H H \R/ I R R n R The basic amine may be designated thus:

subject to what has been said previously as to the presence of a substituted imidazoline or a substituted tetrahydropyrimidine radical having at least one basic secondary amine radical present and that the ring compound, or rather the two occurrences of R jointly with n, be free from a primary amine radical. However, if one attempts to incorporate into the formula a, structure such as a substituted imidazoline or substituted tetrahydropyrimidine such as the following:

III-CH: 02114011 C2H4.N

, condensation subject to the limitation and explanation previously noted.

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

H \NC-N H OH OH OH H H H o o- C-N H H H R R n R OH 1 OH OH OH OH H H H H o 0* oo H H OH H H O R n R R R n As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaledhyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R n R in which R'" is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is 'well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other wcrds, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described. proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one deos not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approxi- 2,679,488 1 l 'l 2 mating 4 phenolic nuclei will have some trimer No. 274,075, describes compounds of the followand pentamer present. Thus, the molecular ing structure: weight may be such that it corresponds to a frac- N tional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found 5 f no reason for using other than those which are lowest in price and most readily available com- D mercially. For purposes of convenience suitable resins are characterized in the following table: where R 1s a member of the class consisting of TABLE I M01. Wt Example 3 Position R derived of R esin Number of R from Molecule phenyl para 3.5 992. tertiary butyl 3. 5 882. 5 secondary butyl 3. 5 882. 5 cyclohexyl 3. 5 l, 025. 5 tertiary amyl ..do 3. 5 959. mixed secondary and ortho. 3.5 805.5

tertiary amyl. propyi para- 3.5 805.5 tertiary hexyl 3. 5 l, 036. 5 3.5 1,100.5 3.5 1, 207.5 3.5 1,344.5 do 3. 5 1, 49s. 5 acetaldehyde 3. 5 945. 5 do 3.5 1, 022.5 d0 3.5 1,330.5 butyra1dehyde 3. 5 1,071. 5 do 3.5 1,145.5 3. 5 1, 455.5 3.5 1,008.5

3.5 1, 055. 5 3.5 1, 303.5 4.2 905.5 4.2 1, 033.4 4.2 1, 430.6 4.8 1, 094.4 tertiary amy 4. 8 l, 189. 6 nonyl 4. s 1, 570. 4

PART 3 hydrocarbon radicals having up to approximately carbon atoms and includes hydroxylated The expression y amidines is mp y hydrocarbon radicals and also hydrocarbon radiin its u ual nse to in i t rin mp un n cals in which the carbon atom chain is interwhich there are present either 5 members or 6 rupted by oxygen; n is the numeral 2 to 3, D is members, and having 2 nitrogen ms separated a member of the class consisting of hydrogen y a single carbon atom S pp y either and organic radicals containing less than 25 cartwo additional carbon atoms or three additional b atoms, composed of the elements from the carbon atoms completing the ring. All the cargroup consisting of C, N, O and H, and B is a bOn atoms may b substituted The nitrogen member of the group consisting of hydrogen and atom of the ring involving W mOnOValent linkhydrocarbon radicals containing less than '7 cars m y be substituted Needless to y. these bon atoms, with the proviso that at least three compounds include members in which the subrr nce f B are hydrogen. S ifiue fi a m y have 0118 more nitrogen The preparation of an imidazoline substituted atoms, either in e form of amino nitrogen in the two-position by lower aliphatic hydrocarafi in the form of acylated nitrogen atoms bon radicals is described in the literature and is These yc i am are sometimes Charreadily carried out by reaction between a monoact i e a being substituted imidazolines and carboxylic acid or ester or amide and a diamine tetrahydropyrirnidines in which the two-position or po1yamine, containing at least one primary carbon 0f the l 8 generally bonded to a amino group, and at least one secondary amino drocarbon radical or comparable radical derived group r a second primary amino group separated om an d, s as a 10W molal fatty acid. a from the first primary amino group by two carhigh molal fatty acid, or comparable acids such bon atoms a polycarboxy acids- Examples of suitable polyamines which can Cyclic amidines obtained from oxidized wax 5 be employed as r t t t form basic nitrogen.-

acids are described in detail in co-pending Blair containing compounds of the present invention application, Serial No. 274,075, filed February 28, include polyalkylene' polyamines such as ethyl- 1952. Instead of being derived from oxidized ene-diamine, diethylenetriamine, triethylenewax acids, the cyclic compounds herein employed tetramine, tetraethylenepentamine, and. higher may be obtained from any acid from acetic acid polyethylene polyamines, and also including 1,2- upward, and may be obtained from acids, such diaminopropane, N-ethylethylenediamine, N,N- as benzoic, or acids in which there is a reocdibutyldiethylenetriamine, 1,2-diaminobutane, curring ether linkage in the acyl radical. In hydroxyethylethylenediamine, lg-propyleneessence then, with this difference said aforetriamine, and the like.

mentioned co-pending Blair application, Serial For details of the preparation of imidazolines application,

, economical for use.

substituted in the 2-position from amines of this type, see the following U. S. Patents: U. S. No. 1,999,989 dated April 30, 1935, Max Bockmuhl et al.; U. S. No. 2,155,877 dated April 25, 1939, Edmund Waldmann, et al.; and U. S. No. 2,155,878 dated April 25, 1939, Edmund Waldmann et a1. Also see Chem. Rev., 32, 47 3).

Equally suitable for use in preparing compounds of my invention and for the preparation of tetrahydropyrimidines substituted in the 2- position are the polyamines containing at least one primary amino group and at least one secondary amino group, or another primary amino group separated from the first primary amino group by three carbon atoms. This reaction is generally carried out by heating the reactants to a temperatureof 230 C. or higher, usually withinthe range of 250 C. to 300 C., at which temperatures water is evolved and ring closure is eifected. For details of the preparation of tetrahydropyrimidines, see German Patent No. 700,371, dated December 18, 1940, to Edmund Waldmann and August Chwala; German Patent No. 701,322 dated January 14, 1941, to Karl Miescher, Ernst Urech, and Willi Klarer; and U. S. Patent No. 2,194,419 dated March 19, 1940, to August Chwala.

Examples of amines suitable for this synthesis include 1,3-propylenediamine, trimethylenediamine, 1,3-diaminobutane, 2,4-diaminopentane, N ethyl trimethylenediamine, N aminoethyltrimethylene diamine, aminopropyl stearylamine, tripropylenetetramine, tetrapropylenepentamine, high boiling polyamines prepared by the condensation of 1,3-propylene dichloride with ammonia, and similar diamines or polyamines in which there occurs at least one primary amino group separated from another primary or secondary amino group by three carbon atoms.

Similarly,- the same class of materials are included as initial reactants in co-pending Smith Serial No. 281,645, filed April 10, 1952. Said application in essence states that the cyclic compounds mployed may be derived from either poylamines in which the nitrogen atoms are separated by an ethylene radical or by a trimethylene radical. Reference to a propylene radical means a methyl substituted ethylene radical, i. e., having only 2 carbon atoms between nitrogen atoms. From a practical standpoint, as will be explained hereinafter, the polyethylene imidazolines are most readily available and most Thus, broadly speaking, using the same terminol y as said Smith application, Serial N 0. 281,645, the present invention is concerned with a condensation reaction, in which one class of reactants are substituted ring compounds consisting of /N /N /N\. /N\ RC/ \R R({ R' R\ /R R\ /R \N/ N N A BL J DIRII S 7R in which R is a divalent alkylene radical selected from the class consisting of -OH2OH2 -oHioHioH=- H COH:

-CH2- H-GH1- divalent, organicradical containing less than 25 group consisting of C, H, O, and N, ing at least one amino group, and R is a member of the class consisting of hydrogen, aliphatic hydrocarbon radicals, hydroxylated aliphatic hydrocarbon radicals, cycloaliphatic hydrocarbon radicals, and hydroxylated cycloaliphatic hydrocarbon radicals; R? is a, member of the class consisting of hydrogen, aliphatic radicals and cycloaliphatic radicals, with the proviso that in the occurrence of the radicals, R and R there be present at least one group of 8 to 32 uninterrupted canbon atoms. In the present instance, however, there is no limitation in regard to the radicals R and R".

What has been said previously in regard to the two above copending applications as far as substituted imidazolines are concerned is substantially the same as appears in Blair and Gross Reissue Patent No. 23,227, reissued May 9, 1950, and Monson Patent No. 2,589,198 dated April 11, 1952.

As to the siX-membered ring compounds generally referred to as substituted pyrimidines, and more particularly as substituted tetrahydropyrimidines, see U. S. Patent No. 2,534,828 dated December 12, 1950, to Mitchell et a1. With the modification as far as the instant application goes, the hydrocarbon group R may have the same variation as when it is part of the fivemembered ring previously referred to and is not limited to an alkyl group having at least 10 carbon atoms as in the instance of the aforementioned U. S. Patent No. 2,534,828.

For the purpose of the present invention there is selected from the broad case of compounds previously described such members as meet the following limitations: (a) Have present at least one basic secondary amino radical; and (b) be free from primary amino groups and especially basic primary amino groups. Such compounds may have two-ring membered radicals present instead of one ring-membered radical and may or may not have present a tertiary amine radical or a hydroxyl radical, such as a hydroxy alkyl'radical. A large number of compounds have been described in the literature meeting the above specifications, of which quite a few appear in the aforementioned issued U. S. patents. Examples selected from the patents include the following:

%NCHQ C11H2a.0 (1) I N lHz 2-undecy1imidazoline %NCH2 CnHmC N-wm 2-heptadecylimidazoline /NOH2 CHEN-6 (3) V N- H) CHI- 2-methy1,1-hexadecy1aminoethylaminoethylimidazoline N- C H:

bHe-N H- 0121115 l-dodecylaminopropylimidazoline 1- (stearoyloxyethyl) aminoethylimidazoline l-stearamidoethylaminoethylimidazoline N--C Hz C I 01114.1? CaH4-NHO C .C H:

1- (N-dodecyl) -aceta.midoethylaminoethylimidazoline H-C Hz 2-heptadecyl,4, 5-dimethylimidazoline N-CH:

l-dodecylaminohexylimidazoline N-CH: 11.6

N-CH:

tHn.NH.C:H4. O 0 0151135 rHAN 2-heptadecyl,l-methylaminoethyl tetrahydropyrimidine 4-methyl,2-dodecyl,l-methylaminoethylamiuoethyl tetrahydropyrimidine As has been pointed out previously, the reactants herein employed may have two substituted imidazoline rings or two substituted tetrahydropyrimidine rings. Such compounds are illus- 15 trated by the following formula:

Such compounds can be derived, of course,

from triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and higher homologues. The substituents may vary depending on the source of the hydrocarbon radical, such as the lower fatty acids and higher fatty acids, a resin acid, naphthenic acid, or the like. The group introduced may or may not contain a hydroxyl radical as in the case of hydroxyacetic acid, acetic acid, ricinoleic acid, oleic acid, etc.

One advantage of a two-ring compound resides in the fact that primary amino groups which constitute the terminal radicals of the parent polyamine, whether a polyethylene amine or polypropylene amine, are converted so asto eliminate the presence of' such primary amino radicals. Thus, the two-membered ring compound meets the previous specification in regard to the nitrogen-containing radicals.

Another procedure to form a two-membered ring compound is to use a dibasic aci Suitable compounds are described, for example, in aforementioned U. S. Patent No. 2,194,419, dated March 19, 1940, to Chwala.

As to compounds having a tertiary amine radical, it is obvious that one can employ derivatives of polyamines in which the terminal groups are unsymmetrically alkylated. Initial poly- 'ene imine, and second, reaction with another 18 amines of this type are illustrated by the follow- Similarly, a compound having no basic secing formula: ondary amino radical but a basic primary amino radical can be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide,

glycide, etc., to yield a perfectly satisfactory re- NCQH4(NC2H4),.N I actant for the herein described condensation 1 procedure. This can be illustrated in the following manner by a compound such as in which R represents a small alkyl radical such as methyl, ethyl, propyl, etc., and n represents a N OH small whole number greater than unity such as ennui-o 2, 3 or 4. Substituted imidazolines can only be formed from that part of the polyamine which has a primary amino group present. There is no objection to the presence of a tertiary amino 2- eptadecyl,l-aminoethylimidazoline radical as previously pointed out. Such derivatives, provided there is more than one secondary amino radical present in the ring compound, may be reacted with an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., so as to convert one or more amino nitrogen radicals into the corresponding hydroxy alkyl radical, provided, however, that there is still a residual secondary amine group. For instance, in the NCH: preceding formula if n represents 4 it means the ring compound would have two secondary nitro- (l6) gen radicals and could be treated with a single NOHI mole of an alkylene oxide and still provide a satis- 4 factory reactant for the herein described con- I densation reaction. I

Ring compounds, such as substituted imidazo- H lines, may be reacted with a substantial amount of alkylene oxide as noted in the preceding paraa duced by two Steps first reactmn with an ethyl above, to wit, 2-heptadecyl,1-aminoethy1imidazmole of the Oxide, or with an alkylating agent oline; for instance, reaction with an alkylene such as dimethyl sulfate, benzyl chloride, a low imine such as etbylene Propylene imine molal ester of a sulfonic acid, an alkyl 40 etc. Ifreacted with ethylene imine the net result mide' etc is to convert a primary amino radical into a see- As to oxyalkylated imidazolines and a Variety onfiary m Ia431E311 d also introduces a new of suitable high molecular weight carboxy acids pnmary ammo group If ethylene umne 15 which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of 2-heptadecyl,l-aminoethylimidazoline, which can be illustrated by the following formula:

which may be the source of a substituent radi p oyed, the net result is i y to F 241923 See 3. Patent 2,468,180, dated April 26 tadecyl,1 ammoethylimidazolme into Z-hepta- 1949, to De Groote and Keisen decyl,1-diethylenediaminoimidazoline. However,

other suitable means may be employed to if propylene imine is used the net result is a comeliminate a terminal primary amino radical. If pound i can be collsldered as being derived there is additionally a basic secondary amino hypothetlcauy from a mlxed pelyalkylene amme radical present then the primary amino radical one having both ethylene groups and a can be subjected to acylation notwithstanding propylene grqup between mtrogqn o sth fact th t th surviving amino group has no A more satisfactory reactant is to employ one significant basicity. As a rule acylation takes Obtained by the n epichlolohyqrin 011 a place at the terminal primary amino group rath secondary al yl amlne, such as the following comthan at the secondary amino group, thus one pound:

can employ a compound such as C2H4\ H H H /NOH: v NCC CH C17H35 6o C: 4

2H4.NH.O2H4.NH2 If a mole of 2-heptadecyl,1-aminoethylimidaz- 2-heptadecyl,l-diethylenediaminolmidazoline Cline is reacted with a mole of the compound just described, to wit, 5 and subject it to acylation so as to obtain, for example, acetylated 2-heptadecyl,1-diethylene- H H H diaminoimidazoline of the following structure: H v

/N-OH2 7 o C17Ha5-C O (15) l the resultant compound has a basic secondary amino group and a basic tertiary amino group. 1H4.NH.C2H4.N\ s e U, s. Patent No. 2,520,093 dated August 22,

H 1 50, to Gross. a v

tions. fined satisfactorily'byformula, although it may For purpose of convenience, what has been said by direct reference is largely by way of illustration in which there is present a sizable hydrophobe group, for instance, heptadecyl groups, pentadecyl groups, octyl groups, nonyl groups, etc. etc.

As has been pointed out, one can obtain all these comparable derivatives from low molal acids, such as acetic, propionic, butyric, valeric, etc. Similarly, one can employ hydroxy acids such as glycolid. acids, lactic acid, etc. Over and above this, one may employ acids which introduce a very distinct hydrophobe effect as, for example, acids prepared by the oxyethylation of a low molal alcohol, such as methyl, ethyl, propyl, or the like, to produce compounds of the formula R (OCHzCHz) nOH in which R is a low molal group, such as methyl, ethyl or propyl, and'n is-a whole number varying from one up to 15 or 20. Such compounds can be converted into the alkoxide and then reacted with an ester of chloracetic, followed by saponification so as to yield compounds of the type R(OCH2CH2)nOCH2COOH in which n has its prior significance. Another procedure is to convert the compound into aihalide ether such as in R.(OCI-IzCI-I2)1,Cl in which n has its prior significance, and then react such halide ether with sodium cyanide so as to give the corresponding nitrile, R(OCH2CH2)1LCN, which can be converted into the corresponding acid, of the following composition R(OCH2CH2)12C@OH. Such acids can also be used to-produce acyl derivatives of the kind previously described in which acetic acid is used as an acylating agent.

What has been said above is intended to emphasize the fact that the nitrogen compounds herein employed can vary from those which are strongly hydrophobe in character and have a minimum hydrophobe property, to those which are essentially hydrophile incharacter and have only a very minimum hydrophobe property.

Examples of decreased hydrop'hobe-character are exemplified by 2-'methylimidazoline,' 2-propylimidazoline, and Z-butylimidazolind, of the following structures:

N-CH:

PART 4 g The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation 'reactionor reac- Since the resin 'molecule cannot bodebe so illustrated in an idealized simplification; it is difiicult to actually depict the final product of the cogeneric mixture except in terms oftheprocess itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or .in the manufacture .of a phenol-amineralde: hyde resin; or else froma particularly selected resin and an amine and formaldehyde in' the man ner described in Bruson Patent vNo. 2,031,'557,'in order to obtaina'heat-reactive resin. Since the condensation products obtained are not heatconvertible and since manufacture is not .restricted to a single phase system, and since ternperatures up to .C. or thereaboutsmay be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pet .of the kind described inaforementioned U. S. Patent No. 2,499,368. inmost instances theresin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; Lin .ifact, usually it is apt to be a solid at distinctly higher temperatures, for instance,-.ordinaryroom temperature. Thus, I have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance,.at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk ofthe reaction,-takes I place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is. soluble onlyin an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that .in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 3'7 or it maybe diluted down to about 30 formaldehyde. However, paraformaldehyde can be used but it is more difiicult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of theprocess, no problem is involved if the material is used for any subsequent oi reaction, However, if the reaction mass is to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is the usual procedure as,

. 21 to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact'that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to. be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the products obtained are, almost invariably a dark red in color or at least a red-amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, 1. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation?; and the third factor is this, (0) is an effort to be made to purify the reaction mass by for example, a waterwash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? cedures are well known and, needless to say, cer- Such protain solvents are more suitable than others. Everything else being equal, I have found xylene the most satisfactory solvent.

I have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear .some' similarity to the present procedure. There is no objection, of course, to giving'the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind; herein described. If a lower temperature reac-- tion is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, I am not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of I unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a twoe phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out I prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an to cover all three forms, 1. e.,

autoclave and :no attempt m e to r move w ter until the reaction is over. Generally Speak-.- ing, such a procedure is much lesssatisfactory fora number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, andother mechanical or chemical difliculties are involved. I have found no advantage in using solid formaldehyde because even here waterof reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction hasproceeded as one can reasonably expect at a low temperature, for in-.- stance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or.5 hours, or at the most, up to -24 hours, I then complete the reaction by raising the temperature up to .150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or .formaldehyde. At a higher temperature I use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. I then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 0., and below 150 C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and. then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants .goes I.have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the sec- .ondarypolyamine and 2 moles of formaldehyde. In someinstanoes I have added a trace of caustic .as .an added catalyst but have found no particular advantage in this. In other cases I have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases Ihave used a slight excess of nitrogen compound and, again, have not found any particular advantage in so doing. Whenever feasible 1 have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and par.- ticularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index. In the hereto attached claims reference is made to the product as such, i. e., the anhydro base. Needless to say, the hydrated base, i. e., thematerial as it combines with water or the salt form, with a combination of suitable acids as noted, is essentially the same material but is merely another form and, thus, the claimsare intended the anhydro base,

the free base, and the salts.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve byway of illustration:

.hours.

cedure is. illustrated by Example 11;

The-phenol-aldehyde resin is the one that has been identified previously as Example 211. It was obtained from a paratertiar-y butyl phenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. Theresin so obtained in a neutral state had .a light amber color.

882 grams of the resin identified as 2a.,preceding, were powdered and mixed with a somewhat lesser amount of xylene, i. e., 600 grams. .The mixture was refluxed until solution was come plete. It was then adjusted to approximately 35 C. and 612 grams of 2-oleylimidazoline, pree viously shown in a structural formula as ring compound (3), were added. The mixture was stirred vigorously and formaldehyde addedslowly. In this particular case the formaldehyde ,used was a 37% solution and 162 grams were added in approximately 3 hours. The mixture was stirred vigorously and kept within a range of approximately 40 to 44 C., forabout 16 /2 hours. At the end of this time it was refluxed, using a phaseeseparating trap anda small amount of aqueous distillate withdrawn from time to time. The presence of .unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear in approximately three hours after refluxing started. ,As soon as the odor of formal.- dehyde was no longer detectible the phaseeseparating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was re.- moved until the temperature reached approxi mately 148 C. The mass was kept at this higher temperature for 3 or4 hours. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated .on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a thicksticky fluid or tacky resin. The overall reaction time was approximately 30 hours. In other examples it varied from as little as 24hours up to approximately 38 h The ti e n b e u d y u tin t e low temperature period to approximately 3 to 6 Note that in Table 11 following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30to 40 C.) for a periodof several hours. Then refluxing was employed unt t o or of mal eh d d ppe ed- A t r t o o orm ldeh de disappea ed th phas separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to 150 0., orthereabouts. Usually the mixture yielded a c ear solutionby the time the bulk of the water, or all of the-water, had been removed.

Notethat as pointed out previously, this pro- 24 examples in 'lable II.

TABLE II Strength of Reac- Reac- Max. Formalde- Solvent Used tion tion Distill hyde Soln. and Amt. Temp., Time Temp., and Amt. 0. (hrs) 0.

37%, 162 g.. Xylene, 600 g 30-25 30 148 37%, 81 g. Xylene, 450 g. 21-23 24 145 do Xylene, 600 g -22 28 150 Xylene, 400 g 22-24 28 148 Xylene, 450 g 21-23 148 Xylene, 600 g 21-25 26 146 Xylene, 400 g 23-28 26 147 Xylene, 450 g 22-26 26 146 Xylene, 600 g 21-25 38 150 Xylene, 450 g 20-24 36 149 Xylene, 500 g.. 21-22 24 142 Xylene, 650 g 20-21 26 145 Xylene, 425 g 22-28 28 146 Xylene, 450 g. 23-30 27 150 ene, 550 g. 20-24 29 147 ylene, 440 g 20-21 30 148 ylene, 480 g. 21-26 32 146 ylene, 600 g. 21-23 26 147 Xylene, 500 g 21-32 29 150 do 21-30 32 150 Xylene, 550 g 21-23 37 150 Xylene, 440 g. 20-22 30 150 do ene, 600 g 20-25 36 149 30%, g Xylene, 400 g 20-24 32 152 The amine numbers referred to are the ring compounds identified previously by number in Part 2.

PART 5 30 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable wellknown classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both 011- and water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicing the present process, the treating or demulsifying agent is used in the conventional way, well known to the art, described, for examp in Patent 29, dated January 27, 1953, Part 3, and reference is made thereto fora description of conventional procedures of demulsifying, including batch, continuous, and downthe-hole demulsification, the process essentially involving introducing a small amount of demulsifler into a large amount of emulsion with. adeor without the application the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

The product of Example 1b, 20%;

A cyclohexylamine salt of a polypropylated napthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid,.12%;

A high-boiling aromatic petroleum solvent, 15%

Isopropyl alcohol, 5%.-

The above proportons are all Weight percents.

The compounds herein described and particularly those adapted for breaking petroleum emulsion although having other uses as noted in my co-pending application, Serial No. 288,746, filed May 19, 1952, are derived from resins in which the bridge between phenolic nuclei is a methylene group or a substituted methylene group.

Comparable amine-modified compounds serving all these various purposes are obtainable from another class of resins, i. e., those in which the phenolic nuclei are separated by a radical having at least a 3-carbon atom chain and are obtained, not by the use of a single aldehyde but by the use of formaldehyde, in combination with a carbonyl compound selected from the class of aldehydes and ketones in which there is an alpha hydrogen atom available as in the case of acetaldehyde or acetone. Such resins almost invariably involve the use of a basic catalyst. Such bridge radicals between phenolic nuclei have either hydroxyl radicals, or carbonyl radicals, or both and are invariably oxyalkylation-susceptible and may also enter into more complicated reactants with basic secondary amines. The bridge radical in the initial resin has distinct hydrophile character. Such resins or compounds which can be readily converted into such resins are described in the following patents. Such analogous compounds are not included as part of the instant invention.

U. S. Patent No. 2,191,802, dated February 2'7, 1940, to Novotny et al.; 2,448,664, dated Septemquate admixture with of heat, and allowing rig-679,488

her '7, 1948, to Fife et al.; 2,538,883, dated January 23, 1951, to Schrimpe;.2,538,884, dated..January 23, 1951, to Schrimpe; 2,545,559, datedMarch 20, 1951, to Schrimpe; 2,570,389, dated October 9, 1951, to Schrimpe.

Having thus described. my invention, what I claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil typecharacterized'by subject to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; saidv resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of theformula in which R, is an aliphatic hydrocarbon radical having at least 4 and not more than Z i-carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and formaldehyde; said condensation reaction being conducted at a ternperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyallr'ylationsusceptible.

2; A process for breaking'petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtainedin the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6' phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence'of trifunctional phenols; said phenol being of the formula- OBL in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substitutedin the 2,4,6position; (b) cyclic amidines selected from the class consisting of substituted imidazolin'es and substituted. tetrahydropyrimidines in which there is present at hydric phenol least one basic secondary amino radical and characterized. by freedom from any. primary. amino radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to pro duce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the further proviso that the ratio of reactants be approximately 1, 2i

and 2 respectively; and'with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible; fusible, non-oxygenated organic solventsoluble, water-insoluble, lowstage phenolformaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin'molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being derived by reaction between a difunctiona1 monoand formaldehyde; said resin being formed in the substantial absence of'trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms andrsubstituted in the 2,4,6 position; (b) cyclic amidines selected from the class consistin of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde derived methylene bridge connecting the. amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants beiapproximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resultingfrom the process be heat-stable and .oxyalkylation-susceptible.

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifierincluding the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble; water-insoluble, low stage phenol-formin which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminat water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connectingthe amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (0) formaldehyde; said condensation 1 reaction being conducted to a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

6. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (b) an oXyethyla'tion-susceptible, fusible, non-oxygenated organic solvent-soluble, Water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difuctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifuctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

'7. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular Weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunc- 3.1 tionaliphcnols said. phenol beingof. the-formulain which R is analiphatic hydrocarbon radical havingat least 4 and not more than 12 carbon atoms and substituted in the para position; (b) a basic hydroxylated cyclic amidine selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical andcharacterized by freedom from any primary amino radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent;

and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

8. The process of claim 1 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro .base as is, (b?) r the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sumcient to produce an emulsion when said xylene solution is shalren vigorously with 1m 3 volumes of'water.

9. The process of claim 2 with the proviso that the hydrophile properties ofthe product of the condensation reaction employed in the form of a member of the class consisting of (w) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

10'. The process. of claim 3 with the proviso that the hydrophileproperties of the product of the condensation reaction employed in the form of a member of the class consisting of (a), the,,-anhydro,base. as.is,- (b) thence/beset and- (c). the, salt. equal weight of. xylene'are sufficient to produce.

an emulsion when said xylene solution .is shaken,-

vigorouslywith l to.3,volumes.o water.

1.1. The process; of claim 4 with the proviso, that the hydrophile.- properties ofv the: product. of the. condensation. reaction employed in...theform of amember, of the. class. consisting, of, (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene aresufficient to produce an emulsion when saidpxylene solution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 5 with the proviso that thehydrophile properties of the productof the condensation reaction employed in the form of a member oftheclass consisting of (a) the anhydro base as is, (b) the'free base,- and (c) the salt of hydroxy acetic acid, in 'anequal weight of xylene are-sufficient to produce an emulsion when said xylene solution is shakenvigorously with l to 3 volumes of water.

13'. The process of claim 6 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form-o1 amember of the class consisting of- (c) the anhydro base as-is, (b) the freebase, and (c) the salt of hydroxyacetic acid, in an equal weight of xylene are-sufficient-toproducean emulsion when said x-ylene solution is-shaken vigorously with l to 3 volumes ofwater.

14. The process of claim '7 with the proviso; that the hydrophile properties of' the, productof the condensation reaction employedintheform of, a member of the class consisting; of (a) the anhydro baseas is, (b the free, base, and (c')- the salt-of hydroxyaceticacid, in an equal weight of xylene are sufficient to produce an emulsion-when saidxylenesolutionis shaken vigorously with 1 to 3'volumes-of'w-ater.

References Cited in the file of, this patent UNITED STATES PATENTS i Number Name. Date.

2,031,557 Bruson Feb. 18, 1936. 2,262,743 DeGjrooteet al., .,Nov. 11, 19.41; 2,292,208 DeGroote. et a1, Aug, 4, 19.4.2. 2357,6534 Bond et a1 Dec, 2.8.1.9 8. 2,499,365 DeGroote et al; Mar. '7, 1950 2,499,368 DeGroote et a1. ,Mar '7, 19.50 2,570,377 Revukas Oct. 9, 1951 2,589,198 Monson. F. Mar. 11, 195.2

oi. hy roxy cetic. acid, in an. 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE PRODUCTS OBTAINED IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 